聚多巴胺修饰金纳米花的可控制备及在光热治疗中的应用

doi:10.7503/cjcu20190488

摘要/Abstract

摘要：

采用无模板法制备了金纳米花, 其形状与粒径大小可以通过改变反应温度和还原剂抗坏血酸的用量来调控; 然后, 通过多巴胺的表面原位聚合反应制备了聚多巴胺修饰的金纳米花, 以提高其在近红外区的吸收能力及生物相容性. 采用透射电子显微镜(TEM)、紫外-可见吸收光谱(UV-Vis)和纳米粒度/Zeta电位仪等对金纳米花和聚多巴胺修饰金纳米花的形态、粒径和光学特性进行了表征; 通过傅里叶变换红外吸收光谱(FTIR)分析证明聚多巴胺修饰成功; X射线衍射(XRD)分析结果表明, 聚多巴胺修饰前后金纳米花的晶体结构未变; 最后, 采用噻唑蓝(MTT)法体外评价了聚多巴胺修饰金纳米花的细胞毒性. 研究结果表明, 反应温度越低, 金纳米花表面分支结构越丰富, 以0 ℃为最佳反应温度; 还原剂抗血酸的用量越高, 金纳米花粒径越小; 金纳米花粒径在60~100 nm范围内可调, 最大吸收波长为575~650 nm. 经聚多巴胺修饰后, 金纳米花的最大吸收波长发生了显著红移(>80 nm), 近红外区的吸收范围显著扩大. 通过调控多巴胺溶液浓度, 可将金纳米花表面聚多巴胺层的厚度控制在8~14 nm. 在808 nm激光辐照下, 聚多巴胺修饰金纳米花溶液可迅速升温至57 ℃. 此外, 细胞实验结果表明, 聚多巴胺修饰后金纳米花的细胞毒性更低. 用其对HeLa肿瘤细胞进行光热治疗后, 细胞存活率仅为10%. 因此, 聚多巴胺修饰金纳米花作为光热试剂在肿瘤治疗领域具有潜在的应用前景.

关键词: 金纳米花, 聚多巴胺, 形貌, 近红外吸收, 光热治疗

Abstract:

Gold nanoflowers(AuNFs) were prepared through template-free method. The size and morphology of AuNFs were modulated by reaction temperature and the amount of reducing agent ascorbic acid. Furthermore, polydopamine(PDA) modification was adopt to improve the near-infrared(NIR) absorbance and biocompatibility of AuNFs. The size, morphology and optical properties of AuNFs and PDA modified AuNFs were characterized by transmission electron microscopy(TEM), dynamic light scattering(DLS) & Zeta potential analyzer and UV-Vis spectroscopy. The modification of PDA was characterized by Fourier transform infrared(FTIR) spectroscopy. The X-ray diffraction(XRD) analysis indicated that the crystal structure of AuNFs had no changes after PDA modification. The cytotoxicity of samples in vitro was evaluated by MTT assay. The results demonstrated that the lower temperature(0 ℃) is the proper reaction temperature to obtain the multi-branched structures of AuNFs. Meanwhile, increasing the concentration of reducing agent ascorbic acid would obtain the smaller AuNFs. The size of AuNFs ranged from 60—100 nm, and the wavelength of UV-Vis absorption peak was 575—650 nm. After PDA modification, the significantly red-shifted(over 80 nm) of UV-Vis absorption was found, and the absorption range in the near infrared region was significantly improved. The thickness of PDA layer outside AuNFs was about 8—14 nm through PDA concentration changes. Under 808 nm laser irradiation, the solution with PDA-AuNFs were rapidly heated to 57 ℃. In addition, the cell viability in vitro demonstrated that the PDA-AuNFs had lower cytotoxicity. After photothermal treatment with PDA-AuNFs, the cell survival of HeLa cells was about 10%. Therefore, the PDA-AuNFs had potential applications as photothermal reagents for tumor therapy.

Key words: Gold nanoflower, Polydopamine, Morphology, Near-infrared absorbance, Photothermal therapy

中图分类号:

O611.3

TrendMD:

邬丰任,刘永佳,陆学民,朱邦尚. 聚多巴胺修饰金纳米花的可控制备及在光热治疗中的应用. 高等学校化学学报, 2020, 41(3): 465.

WU Fengren,LIU Yongjia,LU Xuemin,ZHU Bangshang. Controllable Preparation of Polydopamine Modified Gold Nanoflowers and Its Application in Photothermal Therapy ^†. Chem. J. Chinese Universities, 2020, 41(3): 465.

图/表 8

Fig.1 TEM images(A)—(E) and UV-Vis spectra(F) of AuNFs synthesized at different temperatures Temperature/℃: (A) 0; (B) 10; (C) 20; (D) 30; (E) 40.

Fig.2 TEM images of AuNFs synthesized with different amounts of AA V(AA)/μL: (A) 20; (B) 40; (C) 60; (D) 80.

Fig.3 Hydrodynamic diameter(A), zeta potential(B) and UV-Vis spectra(C) of AuNFs synthesized with 20, 40, 60 and 80 μL AA

Fig.4 FTIR spectra of AuNFs prepared with 20 μL AA(AuNFs20), AuNFs modified with 5 mg/mL DA·HCl(PDA-Au5) and DA·HCl(A) and XRD patterns of standard Au(JCPDS No. 89-3697), AuNFs20 and PDA-Au5(B)

Fig.5 TEM images of AuNFs20(A), PDA-Au1(B), PDA-Au2(C) and PDA-Au5(D)

Fig.6 Hydrodynamic diameters(A), zeta potentials(B) and UV-Vis spectra(C) of AuNFs 20(a), PDA-Au1(b), PDA-Au2(c) and PDA-Au5(d)

Fig.7 Thermal images(A) and temperature-time profiles(B) of H2O(a), AuNFs20(b) and PDA-Au5(c) under irradiation of 808 nm laser(1 W/cm2) for 10 min

Fig.8 Cytotoxicity of HeLa cells cultivated with AuNFs and PDA-Au5 without(A) or with(B) a 10 min laser(1 W/cm2)

参考文献 24

[1]	Jia W. F., Li J. R., Lin G. H., Jiang L ., Cryst. Growth. Des., 2011, 11( 9), 3822— 3827
[2]	Li S. N., Zhang L. Y., Wang T. T., Li L., Su Z. M ., Chem. Commun., 2015, 51( 76), 14338— 14341
[3]	Wang C. R., Yan X. Z., Yu Y. F ., Mater. Res. Innov., 2014, 18( Sup2), 585— 590
[4]	Ong X. Y., Chen S., Nabavi E., Regoutz A., Payne D. J., Elson D. S., Dexter D. T., Dunlnop I. E., Porter A. E ., ACS. Appl. Mater. Inter., 2017, 9( 45), 39259— 39270
[5]	Zhong L., Zhai X. D., Zhu X F., Yao P. P., Liu M. H ., Langmuir, 2010, 26( 8), 5876— 5881
[6]	Feng J. J., Chen S. S., Chen X. L., Zhang X. F., Wang A. J. J ., Colloid Interf. Sci., 2017, 509, 73— 81
[7]	Wang A. J., Qin S. F., Zhou D. L., Cai L. Y., Chen J. R., Feng J. J ., Rsc. Adv., 2013, 3( 34), 14766— 14773
[8]	Jian Y. Y., Deng Z. J., Yang D., Deng X., Li Q., Sha Y. L., Li C. H., Xu D. S ., Nano Res., 2015, 8( 7), 2152— 2161
[9]	Barbosa S., Agrawal A., Rodríguez-Lorenzo L., Alvarez-Puebla R. A., Komowski A., Weller H., Liz-Marzan L. M ., Langmuir, 2010, 26( 18), 14943— 14950
[10]	Han J., Li J. R., Jia W. F., Yao L. M., Li X. Q., Jiang L., Tian Y ., Int. J. Nanomed., 2014, 9, 517— 526
[11]	Kumari S., Singh R. P ., Int. J. Biol. Macromol., 2012, 50( 3), 878— 883
[12]	Zhao L., Sun X., Ji X., Li J., Yang W., Peng X ., J. Phys. Chem. C, 2009, 113, 16645— 16651
[13]	Mao K., Chen Y., Wu Z., Zhou X., Shen A., Hu J ., J. Agric. Food Chem., 2014, 62, 10638— 10645
[14]	Zhao X. M., Qi T. Y., Kong H. F., Hao M., Wang Y. Q., Li J., Liu B. C., Gao Y. Y., Jiang J. L ., Int. J. Nanomed., 2018, 13, 6413— 6428
[15]	Liu Z. G., Qu S. X., Wen J ., Prog. Chem., 2015, 27( 2/3), 212— 219
	( 刘宗光, 屈树新, 翁杰 . 化学进展, 2015, 27( 2/3), 212— 219)
[16]	Liu Y. W., Guo Z ., Chem. J., Chinese Universities, 2015, 36( 7), 1389— 1394
	( 刘宇炜, 郭卓 . 高等学校化学学报, 2015, 36( 7), 1389— 1394)
[17]	Khlebtsov B. N., Burov A. M., Khlebtsov N. G ., Appl. Mater. Today, 2019, 15, 67— 76
[18]	Jiang Y. Y., Wu X. J., Li Q., Li J. J., Xu D. S ., Nanotechnology, 2011, 22( 38), 385601
[19]	Luo Y. S., Ji X. H., Zhuang J. Q., Yang W. S ., Colloid Surface A, 2014, 463, 28— 36
[20]	de Vries W. C., Niehues M., Wissing M., Wurthwein T., Masing F., Fallnich C., Studer A., Ravoo J. J ., Nanoscale, 2019, 11( 19), 9384— 9391
[21]	Garrido C., Wsiss-Lopez B. E., Vallette M. M. C ., Spectrosc. Lett., 2016, 49( 1), 11— 18
[22]	Chen W. F., Qin M., Chen X. Y., Wang Q., Zhang Z. R., Sun X ., Theranostics, 2018, 8( 8), 2229— 2241
[23]	Poinard B., Neo S. Z. Y., Yeo E. L. L., Heng H. P. S., Neoh K. G., Kah J. C. Y ., ACS Appl. Mater. Inter., 2018, 10( 25), 21125— 21136
[24]	Fu J. W., Chen Z. H., Wang M. H., Liu S. J., Zhang J. H., Zhang J. N., Han R. P., Xu Q ., Chem. Eng. J., 2015, 259, 53— 61